WO2016056608A1 - バイオマス固体燃料 - Google Patents
バイオマス固体燃料 Download PDFInfo
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- WO2016056608A1 WO2016056608A1 PCT/JP2015/078552 JP2015078552W WO2016056608A1 WO 2016056608 A1 WO2016056608 A1 WO 2016056608A1 JP 2015078552 W JP2015078552 W JP 2015078552W WO 2016056608 A1 WO2016056608 A1 WO 2016056608A1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
- C10L5/40—Solid fuels essentially based on materials of non-mineral origin
- C10L5/44—Solid fuels essentially based on materials of non-mineral origin on vegetable substances
- C10L5/442—Wood or forestry waste
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
- C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
- C10L5/06—Methods of shaping, e.g. pelletizing or briquetting
- C10L5/08—Methods of shaping, e.g. pelletizing or briquetting without the aid of extraneous binders
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
- C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
- C10L5/26—After-treatment of the shaped fuels, e.g. briquettes
- C10L5/28—Heating the shaped fuels, e.g. briquettes; Coking the binders
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
- C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
- C10L5/34—Other details of the shaped fuels, e.g. briquettes
- C10L5/36—Shape
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
- C10L5/40—Solid fuels essentially based on materials of non-mineral origin
- C10L5/44—Solid fuels essentially based on materials of non-mineral origin on vegetable substances
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
- C10L5/40—Solid fuels essentially based on materials of non-mineral origin
- C10L5/44—Solid fuels essentially based on materials of non-mineral origin on vegetable substances
- C10L5/445—Agricultural waste, e.g. corn crops, grass clippings, nut shells or oil pressing residues
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2200/00—Components of fuel compositions
- C10L2200/04—Organic compounds
- C10L2200/0461—Fractions defined by their origin
- C10L2200/0469—Renewables or materials of biological origin
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/06—Heat exchange, direct or indirect
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/28—Cutting, disintegrating, shredding or grinding
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/32—Molding or moulds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
- C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
- C10L5/34—Other details of the shaped fuels, e.g. briquettes
- C10L5/36—Shape
- C10L5/363—Pellets or granulates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Definitions
- the present invention relates to a biomass solid fuel.
- the present invention has been made to solve this problem, and an object of the present invention is to provide a biomass solid fuel that suppresses collapse due to rainwater and reduces COD of wastewater while suppressing cost increase. It is in.
- the biomass solid fuel of the present invention is Fuel ratio (fixed carbon / volatile content) of 0.2 to 0.8, anhydrous base high calorific value of 4800 to 7000 (kcal / kg), oxygen O to carbon C molar ratio O / C of 0.1 to 0 7.
- a molar ratio H / C of hydrogen H to carbon C is 0.8 to 1.3, and it is a biomass solid fuel formed from biomass powder.
- the present invention it is possible to provide a biomass solid fuel that suppresses cost increase, suppresses collapse due to rainwater, and reduces COD of wastewater without using a steam explosion process or a binder.
- the biomass solid fuel of the present invention is obtained through a molding process of crushing biomass after crushing, compressing and molding the biomass that has become scrap or powder into a lump, and a heating process for heating the lump after the molding process
- the molded solid material thus produced is used as fuel (corresponding to PBT described later). Since the biomass solid fuel of the present invention does not require a steam explosion process and a binder, cost increase can be suppressed.
- the block obtained by the molding process and before the heating step is also referred to as “unheated block”.
- the biomass used as the raw material may be woody or grassy, and the tree species and parts thereof are not particularly limited. Examples include bark, walnut shell, sago palm, EFB (empty fruit bunch of palm oil processing residue), meranti, rubber tree and the like, and may be one kind or a mixture of two or more kinds.
- a block is formed using a known molding technique.
- the lump is preferably a pellet or briquette and can be of any size.
- the heating step the molded lump is heated.
- the biomass solid fuel obtained after the heating step preferably has an immersion water COD (chemical oxygen demand) of 3000 ppm or less when immersed in water.
- the biomass solid fuel preferably has a COD ratio represented by (COD of biomass solid fuel after heating step / COD of unheated biomass solid fuel) of 0.98 or less.
- COD chemical oxygen demand
- COD chemical oxygen demand of immersion water when biomass solid fuel is immersed in water
- COD refers to the preparation of an immersion water sample for COD measurement in 1973. This is the COD value analyzed according to JIS K0102 (2010) -17, in accordance with the Agency Notification No. 13 (b) Method for testing metals contained in industrial waste.
- the biomass solid fuel obtained after the heating step preferably has a grindability index (HGI) based on JIS M 8801 of 15 or more and 60 or less, and more preferably 20 or more and 60 or less.
- HGI grindability index
- the BET specific surface area is preferably from 0.15 to 0.8 m 2 / g, more preferably from 0.15 to 0.7 m 2 / g.
- the equilibrium moisture after immersion in water is preferably 15 to 65 wt%, and more preferably 15 to 60 wt%.
- the biomass solid fuel of the present invention has a fuel ratio (fixed carbon / volatile content) of 0.2 to 0.8, an anhydrous base high calorific value of 4800 to 7000 (kcal / kg), a molar ratio of oxygen O to carbon C, O / C is 0.1 to 0.7, and the molar ratio H / C of hydrogen H to carbon C is 0.8 to 1.3.
- the biomass solid fuel of the present invention can be obtained, for example, by adjusting the species of biomass used as a raw material, its part, the heating temperature in the heating step, and the like.
- the industrial analysis values, elemental analysis values, and higher calorific values in this specification are based on JIS M 8812, 8813, and 8814.
- the method for producing a biomass solid fuel according to the present invention includes a molding step of forming biomass powder of crushed and pulverized biomass to obtain an unheated lump, and a heating step of heating the unheated lump to obtain a heated solid matter.
- the heating temperature in the heating step is preferably 150 ° C. to 400 ° C. By setting the temperature of the heating step within this range, a biomass solid fuel having the above characteristics can be obtained.
- the heating temperature is appropriately determined depending on the shape and size of the biomass as a raw material and the lump, but is preferably 150 to 400 ° C, more preferably 200 to 350 ° C. More preferably, it is 230 to 300 ° C. More preferably, it is 250 to 290 ° C.
- the heating time in the heating step is not particularly limited, but is preferably 0.2 to 3 hours.
- the particle size of the biomass powder is not particularly limited, but is about 100 to 3000 ⁇ m on average, preferably 400 to 1000 ⁇ m on average.
- the measuring method of the particle size of biomass powder may use a well-known measuring method.
- the connection or adhesion between the biomass powders is maintained by solid crosslinking, so the particle size of the biomass powders is not particularly limited as long as it can be molded.
- a known range may be used as long as the particle size is in a range where both cost and moldability are compatible.
- B / A 0.7 to 1 where A is the bulk density of the unheated mass before the heating step and B is the bulk density of the heated solid after the heating step.
- the value of the bulk density A is not particularly limited as long as it is a known range in which biomass powder is molded to obtain an unheated lump. Moreover, since the bulk density changes depending on the type of raw material biomass, it may be set as appropriate.
- H2 / H1 1.1 to 2.5, where HGI of the unheated mass (hard glove grindability index of JIS M8801) is H1, and HGI of the heated solid is H2.
- the characteristics of the biomass solid fuel may be determined within a suitable range depending on the species of biomass used as a raw material.
- One example will be described below, but the present invention is not limited to these tree species and combinations thereof.
- preferable ranges are shown for the types of biomass raw materials used in the present invention, the properties of the obtained solid fuel (corresponding to PBT described later), and the production method thereof.
- COD is preferably 1000 ppm or less, more preferably 900 ppm or less, further preferably 800 ppm or less, and the COD ratio is preferably 0.80 or less, more preferably 0.70 or less, and even more preferably 0.68 or less.
- the equilibrium moisture after immersion in water is preferably 15 wt% to 45 wt%, more preferably 18 wt% to 35 wt%, and further preferably 18 wt% to 32 wt%.
- the BET specific surface area is 0.25m 2 /g ⁇ 0.8m 2 / g, more preferably 0.28m 2 /g ⁇ 0.6m 2 / g, 0.32m 2 / g ⁇ More preferably, it is 0.5 m 2 / g.
- HGI is preferably 20 to 60, more preferably 20 to 55, and still more preferably 22 to 55.
- the HGI of coal (bituminous coal) suitable as a boiler fuel for power generation is around 50, and the closer to around 50 is preferable, considering that it is mixed and ground with coal.
- the HGI ratio (described later) is preferably 1.0 to 2.5.
- the fuel ratio is preferably 0.2 to 0.8, more preferably 0.2 to 0.7, and still more preferably 0.2 to 0.65.
- the anhydrous base high calorific value is preferably 4800 to 7000 kcal / kg, more preferably 4900 to 7000 kcal / kg, and further preferably 4950 to 7000 kcal / kg.
- the molar ratio O / C of oxygen O to carbon C is preferably 0.1 to 0.62, more preferably 0.1 to 0.61, and further preferably 0.1 to 0.60.
- the molar ratio H / C between hydrogen H and carbon C is preferably 0.8 to 1.3, more preferably 0.85 to 1.3, and even more preferably 0.9 to 1.3.
- the heating temperature in the heating step is preferably 200 to 350 ° C, more preferably 210 to 330 ° C, and further preferably 220 to 300 ° C.
- solid fuel B a biomass solid fuel (hereinafter sometimes referred to as solid fuel B) when the raw material is European red pine are as follows.
- COD is preferably 900 ppm or less, more preferably 800 ppm or less, further preferably 700 ppm or less, and the COD ratio is preferably 0.75 or less, more preferably 0.68 or less, and even more preferably 0.64 or less.
- the equilibrium moisture after immersion in water is preferably 15 wt% to 45 wt%, more preferably 18 wt% to 40 wt%, and even more preferably 18 wt% to 31 wt%.
- the BET specific surface area is 0.30m 2 /g ⁇ 0.7m 2 / g, more preferably 0.30m 2 /g ⁇ 0.6m 2 / g, 0.30m 2 / g ⁇ More preferably, it is 0.5 m 2 / g.
- HGI is preferably 25 to 60, more preferably 30 to 55, and even more preferably 35 to 55.
- the HGI ratio (described later) is preferably 1.0 to 2.5.
- the fuel ratio is preferably 0.2 to 0.8, more preferably 0.2 to 0.7, and still more preferably 0.2 to 0.65.
- the anhydrous base high calorific value is preferably 4950 to 7000 kcal / kg, more preferably 5000 to 7000 kcal / kg, and further preferably 5100 to 7000 kcal / kg.
- the molar ratio O / C of oxygen O to carbon C is preferably 0.1 to 0.60, more preferably 0.2 to 0.60, and still more preferably 0.3 to 0.60.
- the molar ratio H / C between hydrogen H and carbon C is preferably 0.8 to 1.3, more preferably 0.85 to 1.3, and even more preferably 0.9 to 1.3.
- the heating temperature in the heating step is preferably 200 to 350 ° C., more preferably 220 to 300 ° C., and further preferably 240 to 290 ° C.
- solid fuel C As one aspect of the present invention, the properties of a biomass solid fuel (hereinafter sometimes referred to as solid fuel C) when the raw material is an almond old tree are as follows.
- COD is preferably 2100 ppm or less, more preferably 2000 ppm or less, further preferably 1500 ppm or less, and the COD ratio is preferably 0.80 or less, more preferably 0.75 or less, and further preferably 0.55 or less.
- the equilibrium moisture after immersion in water is preferably 25 wt% to 60 wt%, more preferably 30 wt% to 50 wt%, and even more preferably 30 wt% to 45 wt%.
- the BET specific surface area is 0.20m 2 /g ⁇ 0.70m 2 / g, more preferably 0.22m 2 /g ⁇ 0.65m 2 / g, 0.25m 2 / g ⁇ More preferably, it is 0.60 m 2 / g.
- HGI is preferably 15 to 60, more preferably 18 to 55, and still more preferably 20 to 55.
- the HGI ratio (described later) is preferably 1.0 to 2.0.
- the fuel ratio is preferably 0.2 to 0.8, more preferably 0.25 to 0.7, and further preferably 0.30 to 0.65.
- the anhydrous base high calorific value is preferably 4800 to 7000 kcal / kg, more preferably 4800 to 6500 kcal / kg, and further preferably 4900 to 6500 kcal / kg.
- the molar ratio O / C of oxygen O to carbon C is preferably 0.10 to 0.70, more preferably 0.20 to 0.60, and still more preferably 0.30 to 0.60.
- the molar ratio H / C of hydrogen H to carbon C is preferably 0.8 to 1.3, more preferably 0.85 to 1.3, and still more preferably 0.9 to 1.20.
- the heating temperature in the heating step is preferably 200 to 350 ° C., more preferably 220 to 300 ° C., and further preferably 240 to 290 ° C.
- solid fuel D A mixture of almond shells and old almond wood: solid fuel D
- the properties of a biomass solid fuel (hereinafter sometimes referred to as solid fuel D) when the raw material is a mixture of almond shells and almond old wood are as follows.
- COD is preferably 2500 ppm or less, more preferably 2000 ppm or less, further preferably 1500 ppm or less, and the COD ratio is preferably 0.75 or less, more preferably 0.68 or less, and further preferably 0.50 or less.
- the equilibrium moisture after immersion in water is preferably 15 wt% to 50 wt%, more preferably 20 wt% to 40 wt%, and even more preferably 20 wt% to 35 wt%.
- the BET specific surface area is 0.20m 2 /g ⁇ 0.70m 2 / g, more preferably 0.27m 2 /g ⁇ 0.70m 2 / g, 0.30m 2 / g ⁇ More preferably, it is 0.60 m 2 / g.
- HGI is preferably 20 to 60, more preferably 20 to 55, and still more preferably 23 to 55.
- the HGI ratio (described later) is preferably 1.0 to 2.0.
- the fuel ratio is preferably 0.2 to 0.8, more preferably 0.30 to 0.7, and still more preferably 0.35 to 0.65.
- the anhydrous base high calorific value is preferably 4800 to 7000 kcal / kg, more preferably 4800 to 6500 kcal / kg, and further preferably 4900 to 6300 kcal / kg.
- the molar ratio O / C of oxygen O to carbon C is preferably 0.10 to 0.70, more preferably 0.20 to 0.60, and still more preferably 0.30 to 0.55.
- the molar ratio H / C between hydrogen H and carbon C is preferably 0.8 to 1.3, more preferably 0.8 to 1.25, and even more preferably 0.85 to 1.20.
- the heating temperature in the heating step is preferably 200 to 350 ° C, more preferably 220 to 300 ° C, and further preferably 240 to 290 ° C.
- Solid Fuel E As one aspect of the present invention, the properties of a biomass solid fuel (hereinafter sometimes referred to as solid fuel E) when the raw material is an acacia xylem are as follows.
- COD is preferably 950 ppm or less, more preferably 850 ppm or less, further preferably 800 ppm or less, and the COD ratio is preferably 0.95 or less, more preferably 0.85 or less, and even more preferably 0.80 or less.
- the equilibrium moisture after immersion in water is preferably 20 wt% to 60 wt%, more preferably 20 wt% to 55 wt%, and even more preferably 23 wt% to 53 wt%.
- the BET specific surface area is 0.40m 2 /g ⁇ 0.70m 2 / g, more preferably 0.50m 2 /g ⁇ 0.70m 2 / g, 0.55m 2 / g ⁇ More preferably, it is 0.70 m 2 / g.
- the fuel ratio is preferably 0.2 to 0.6, more preferably 0.2 to 0.5, and still more preferably 0.2 to 0.4.
- the anhydrous base high calorific value is preferably 4800 to 7000 kcal / kg, more preferably 4800 to 6000 kcal / kg, and further preferably 4800 to 5500 kcal / kg.
- the molar ratio O / C of oxygen O to carbon C is preferably 0.40 to 0.70, more preferably 0.45 to 0.70, and still more preferably 0.48 to 0.65.
- the molar ratio H / C between hydrogen H and carbon C is preferably 0.8 to 1.3, more preferably 1.0 to 1.3, and even more preferably 1.1 to 1.3.
- the heating temperature in the heating step is preferably 200 to 350 ° C., more preferably 220 to 300 ° C., and further preferably 240 to 290 ° C.
- COD is preferably 2500 ppm or less, more preferably 2000 ppm or less, further preferably 1200 ppm or less, and the COD ratio is preferably 0.30 or less, more preferably 0.20 or less, and further preferably 0.15 or less.
- the equilibrium moisture after immersion in water is preferably 15 wt% to 50 wt%, more preferably 20 wt% to 45 wt%, and even more preferably 25 wt% to 40 wt%.
- the BET specific surface area is 0.35m 2 /g ⁇ 0.55m 2 / g, more preferably 0.40m 2 /g ⁇ 0.55m 2 / g, 0.40m 2 / g ⁇ More preferably, it is 0.50 m 2 / g.
- the fuel ratio is preferably 0.4 to 0.8, more preferably 0.42 to 0.75, and still more preferably 0.45 to 0.75.
- the anhydrous base high calorific value is preferably 4800 to 7000 kcal / kg, more preferably 5000 to 7000 kcal / kg, and further preferably 5200 to 6500 kcal / kg.
- the molar ratio O / C of oxygen O to carbon C is preferably 0.25 to 0.60, more preferably 0.30 to 0.60, and still more preferably 0.30 to 0.55.
- the molar ratio H / C between hydrogen H and carbon C is preferably 0.8 to 1.3, more preferably 0.8 to 1.2, and still more preferably 0.9 to 1.2.
- the heating temperature in the heating step is preferably 200 to 350 ° C., more preferably 220 to 300 ° C., and further preferably 240 to 290 ° C.
- solid fuel G (Almond shell and walnut shell mixture: solid fuel G)
- the properties of a biomass solid fuel (hereinafter sometimes referred to as solid fuel G) when the raw material is a mixture of almond shells and walnut shells are as follows.
- COD is preferably 2500 ppm or less, more preferably 2100 ppm or less, further preferably 1500 ppm or less, and the COD ratio is preferably 0.65 or less, more preferably 0.55 or less, and further preferably 0.45 or less.
- the equilibrium moisture after immersion in water is preferably 20 wt% to 45 wt%, more preferably 20 wt% to 40 wt%, and even more preferably 25 wt% to 35 wt%.
- the BET specific surface area is 0.15m 2 /g ⁇ 0.35m 2 / g, more preferably 0.19m 2 /g ⁇ 0.33m 2 / g, 0.20m 2 / g ⁇ More preferably, it is 0.30 m 2 / g.
- the HGI is preferably 18 to 60, more preferably 20 to 60.
- the HGI ratio is preferably 1.0 or more.
- the fuel ratio is preferably 0.2 to 0.7, more preferably 0.25 to 0.65, and further preferably 0.28 to 0.60.
- the anhydrous base high calorific value is preferably 4800 to 7000 kcal / kg, more preferably 4800 to 6000 kcal / kg, and further preferably 5000 to 6000 kcal / kg.
- the molar ratio O / C of oxygen O to carbon C is preferably 0.30 to 0.65, more preferably 0.40 to 0.70, and still more preferably 0.40 to 0.60.
- the molar ratio H / C between hydrogen H and carbon C is preferably 0.8 to 1.3, more preferably 0.9 to 1.25, and even more preferably 0.9 to 1.2.
- the heating temperature in the heating step is preferably 200 to 350 ° C., more preferably 220 to 300 ° C., and further preferably 240 to 290 ° C.
- Solid fuel H As one aspect of the present invention, the properties of a biomass solid fuel (hereinafter sometimes referred to as solid fuel H) when the raw material is sago palm are as follows.
- COD is preferably 2000 ppm or less, more preferably 1600 ppm or less, further preferably 800 ppm or less, and the COD ratio is preferably 0.85 or less, more preferably 0.60 or less, and further preferably 0.4 or less.
- the equilibrium moisture after immersion in water is preferably 20 wt% to 35 wt%, more preferably 20 wt% to 33 wt%, and even more preferably 22 wt% to 30 wt%.
- the BET specific surface area is 0.15m 2 /g ⁇ 0.35m 2 / g, more preferably 0.18m 2 /g ⁇ 0.33m 2 / g, 0.18m 2 / g ⁇ More preferably, it is 0.30 m 2 / g.
- the HGI is preferably 20 to 60, more preferably 25 to 55, and even more preferably 30 to 55.
- the HGI ratio is preferably 1.0 to 2.5, more preferably 1.3 to 2.3, and still more preferably 1.5 to 2.2.
- the fuel ratio is preferably 0.2 to 0.8, more preferably 0.25 to 0.8, and even more preferably 0.5 to 0.8.
- the anhydrous base high calorific value is preferably 4800 to 7000 kcal / kg, more preferably 4900 to 6500 kcal / kg, and further preferably 5000 to 6000 kcal / kg.
- the molar ratio O / C of oxygen O to carbon C is preferably 0.20 to 0.65, more preferably 0.20 to 0.60, and still more preferably 0.2 to 0.55.
- the molar ratio H / C of hydrogen H to carbon C is preferably 0.8 to 1.3, more preferably 0.85 to 1.3, and still more preferably 0.85 to 1.2.
- the heating temperature in the heating step is preferably 200 to 350 ° C., more preferably 220 to 300 ° C., and further preferably 240 to 290 ° C.
- EFB Solid Fuel I
- solid fuel I the properties of biomass solid fuel (hereinafter sometimes referred to as solid fuel I) when the raw material is EFB (empty fruit bunch of palm oil processing residue) are as follows.
- COD is preferably 2350 ppm or less, more preferably 2300 ppm or less, further preferably 2000 ppm or less, and the COD ratio is preferably 0.98 or less, more preferably 0.96 or less, and further preferably 0.85 or less.
- the equilibrium moisture after immersion in water is preferably 23 wt% to 45 wt%, more preferably 20 wt% to 40 wt%, and even more preferably 20 wt% to 35 wt%.
- the BET specific surface area is 0.25m 2 /g ⁇ 0.65m 2 / g, more preferably 0.30m 2 /g ⁇ 0.60m 2 / g, 0.35m 2 / g ⁇ More preferably, it is 0.55 m 2 / g.
- the fuel ratio is preferably 0.25 to 0.8, more preferably 0.30 to 0.8, and still more preferably 0.36 to 0.8.
- the anhydrous base high calorific value is preferably 4800 to 7000 kcal / kg, more preferably 4900 to 7000 kcal / kg, and further preferably 5000 to 7000 kcal / kg.
- the molar ratio O / C of oxygen O to carbon C is preferably 0.15 to 0.65, more preferably 0.15 to 0.60, and still more preferably 0.15 to 0.55.
- the molar ratio H / C between hydrogen H and carbon C is preferably 0.5 to 1.3, more preferably 0.55 to 1.3, and even more preferably 0.6 to 1.2.
- the heating temperature in the heating step is preferably 200 to 350 ° C., more preferably 220 to 300 ° C., and further preferably 240 to 260 ° C.
- Solid fuel J As one aspect of the present invention, the properties of a biomass solid fuel (hereinafter sometimes referred to as solid fuel J) when the raw material is meranti are as follows.
- COD is preferably 330 ppm or less, more preferably 320 ppm or less, further preferably 300 ppm or less, and the COD ratio is preferably 0.98 or less, more preferably 0.95 or less, and even more preferably 0.90 or less.
- the equilibrium moisture after immersion in water is preferably 15 wt% to 30 wt%, more preferably 15 wt% to 27 wt%, and even more preferably 18 wt% to 25 wt%.
- the fuel ratio is preferably 0.2 to 0.6, more preferably 0.2 to 0.5, and further preferably 0.2 to 0.45.
- the anhydrous base high calorific value is preferably 4800 to 7000 kcal / kg, more preferably 4800 to 6500 kcal / kg, and further preferably 4800 to 6000 kcal / kg.
- the molar ratio O / C of oxygen O to carbon C is preferably 0.3 to 0.60, more preferably 0.35 to 0.60, and still more preferably 0.40 to 0.60.
- the molar ratio H / C between hydrogen H and carbon C is preferably 0.9 to 1.2, more preferably 0.95 to 1.2, and even more preferably 1.0 to 1.2.
- the heating temperature in the heating step is preferably 200 to 350 ° C., more preferably 220 to 300 ° C., and further preferably 230 to 290 ° C.
- the fuel ratio is preferably 0.2 to 0.8, more preferably 0.2 to 0.7.
- the anhydrous base high calorific value is preferably 4800 to 7000 kcal / kg.
- the molar ratio O / C of oxygen O to carbon C is preferably 0.1 to 0.7.
- the molar ratio H / C between hydrogen H and carbon C is preferably 0.8 to 1.3.
- the heating temperature in the heating step is preferably 200 to 350 ° C., more preferably 220 to 300 ° C., and further preferably 230 to 290 ° C.
- the present inventors in the order of the process of performing the heating process of heating the unheated lump after the molding process, the components derived from biomass that is the raw material without using a binder. It is speculated that a biomass solid fuel with high water resistance can be produced that is used to maintain the connection or adhesion between biomass powders and does not collapse even when immersed in water. As a result of the analysis by the present inventors, the following knowledge about the mechanism by which the biomass solid fuel acquires water resistance was obtained.
- the present inventors have prepared three types of biomass solid fuels having different production methods, specifically, unheated solid fuel obtained by molding pulverized biomass (White Pellet: hereinafter sometimes referred to as WP), and pulverization.
- the solid fuel (Pelletizing Before Torrefaction: hereinafter sometimes referred to as PBT) obtained by molding and heating the formed biomass is subjected to FT-IR analysis, GC-MS analysis, SEM observation, etc. The mechanism of water resistance of the fuel was analyzed. Note that no binder is used in either WP or PBT.
- abietic acid etc. terpenes such as abietic acid and its derivatives
- FIG. 18 is a diagram showing a mechanism (estimation) of solid bridge development in PBT.
- biomass powder in which the liquid due to melting of abietic acid is pulverized as the temperature rises (consolidated by molding after pulverization, Elution into the gap between adjacent biomass powders, evaporation of abietic acid and thermal decomposition occur, and the hydrophobic substance adheres to the gap between the biomass powders to develop crosslinking (solid crosslinking).
- attachment of biomass powder is maintained by the abietic acid derived from the biomass etc. which are raw materials, without adding a binder. Therefore, it is considered that the biomass powders are connected or adhered to each other to suppress water entry and improve water resistance.
- Abietic acid or a derivative thereof has a melting point of about 139 to 142 ° C and a boiling point of about 250 ° C. Therefore, it is inferred that heating causes abietic acid or the like to melt near the melting point to cause liquid crosslinking, and abietic acid or the like thermally decomposes near the boiling point to develop solid crosslinking.
- Terpenes such as abietic acid are generally contained in biomass (Hokkaido Prefectural Forest Products Experiment Station Monthly Report No. 171, April 1966, Japan Wood Conservation Society “Wood Preservation” Vol. 34-2 (2008), etc.) . Although there is a slight difference in content depending on the type of biomass ("Use of essential oil", Oohiro Goro, Report of the 6th Research Subcommittee of the Japan Wood Society, Table 1, Table 1 of the Japan Wood Society 1999), etc. ⁇ Example A> to ⁇ In all of Examples I>, since water resistance (not disintegrated even after immersion in water, see Table 6) is exhibited by heating at 230 ° C. or higher, water resistance is generally increased by heating at least 230 ° C. to 250 ° C. for biomass in general. It is considered to be granted.
- FIG. 19 to 22 are diagrams showing the results of FT-IR analysis of the biomass solid fuel of the present invention.
- the raw material was European red pine of Example B below, which was obtained by analyzing a solid fuel (PBT) obtained by heating at 250 ° C., which was formed into a pellet after pulverization. The same raw material is pulverized and unheated after molding (WP) is also shown.
- PBT solid fuel
- WP unheated after molding
- FIG. 23 is a diagram showing the results of GC-MS analysis of an acetone extract.
- the raw material is the European red pine of Example B as in FIGS. 19 to 22 above, and the solid fuel (PBT) heated at 250 ° C. after being crushed and formed into pellets and unheated (WP) are used. It was.
- PBT solid fuel
- the amount of elution of abietic acid, which is a kind of terpene, into acetone is less than that of WP, and abietic acid is melted by heating to form a liquid bridge, and then volatilization of abietic acid, etc. This is considered to indicate that a solid bridge is formed.
- PBT also improves the strength of solid fuel due to the development of solid cross-linking, and has good grindability without adding a binder by heating at least 230 ° C to 250 ° C as well as water resistance (HGI, grinding speed described later). And it is inferred that good handling properties (a pulverization test described later) can be obtained. Furthermore, as described above, COD is reduced in PBT. This is because the tar content of the biomass raw material is volatilized by heating, and at the same time, the solid fuel surface of PBT is covered with solidified abietic acid, and the solid fuel surface is hydrophobic. This is considered to be because the elution of tar remaining in the biomass raw material is suppressed.
- Example A (Examples A-1 to A-6)
- the biomass was crushed and then pulverized, and a biomass solid fuel A (PBT) was obtained through a molding process for molding the pulverized biomass and a subsequent heating process.
- No binder is used in any step.
- a raw material biomass a mixture of 40% by weight of rice pine, 58% by weight of rice bran, 1% by weight of cedar, and 1% by weight of straw was used. In the molding process of each example, it was molded into a pellet shape having a diameter of 8 mm.
- Comparative Example A is an unheated biomass solid fuel (WP) that has been molded after crushing and pulverization and has not undergone a heating step. In Comparative Example A, no binder is used. The raw material biomass is the same as in Example A-1. The properties of the solid fuel of Comparative Example A are also shown in Table 1.
- HGI is based on JIS M 8801, and the higher the value, the better the grindability.
- Table 1 also shows the results of the higher calorific value (anhydrous basis), the fuel ratio calculated based on the industrial analysis value (air-dry basis), and the elemental analysis value (air-dry basis), and the oxygen O obtained based on this. , Carbon C, and hydrogen H, respectively.
- FIG. 1 shows the correlation between the heating temperature in the heating step and the COD (chemical oxygen demand) and pH of the immersion water when the obtained biomass solid fuel is immersed in water (the pH will be described later).
- the preparation of the immersion water sample for COD measurement was conducted according to JIS K0102 (2010) -17 according to the test method of metals, etc. contained in the environmental waste notification No. 13 (ii) industrial waste in 1973.
- the COD of Comparative Example A is a high value of about 1200 ppm.
- biomass solid fuel heated at 230 ° C. or higher had a COD of 800 ppm or less, indicating that tar content was low. Therefore, it has been shown that the biomass solid fuels of Examples A-1 to A-6 are fuels that have less tar content and excellent handling properties even during outdoor storage. Note that the COD of the biomass solid fuels of Examples A-1 to A-6 heated at 230 ° C. or higher decreased as the heating temperature increased. This is because the COD value is reduced due to volatilization of tar content and the like accompanying heating.
- FIG. 2 shows the correlation between the heating temperature in the heating step, the pulverization property (HGI) of the obtained biomass solid fuel A, and the pulverization rate (described later), and the biomass solid fuels of Comparative Example A and Examples A-1 to A-6 It is a figure shown about.
- HGI pulverization property
- the pulverization speed in FIG. 2 was measured by measuring the weight (g / min) per unit time by measuring the weight of a 700 cc sample that was pulverized by a ball mill and passing through a 150 ⁇ m sieve as the sample after pulverization. Is.
- the ball mill is compliant with JIS M4002, and is used in a cylindrical container having an inner diameter of 305 mm ⁇ axial length of 305 mm.
- the standard grade ball bearings defined in JIS B1501 ( ⁇ 36.5 mm ⁇ 43, ⁇ 30.2 mm ⁇ 67, ⁇ 24.4 mm ⁇ 10 pieces, ⁇ 19.1 mm ⁇ 71 pieces, ⁇ 15.9 mm ⁇ 94 pieces), and rotated at a speed of 70 rpm for measurement.
- the pulverization rate is improved by heating, and the pulverization rate is rapidly increased particularly by heating at 230 ° C. or higher. It can be said that the pulverization rate of the biomass solid fuel A is increased and the pulverization rate is improved by elution and solidification of organic components such as tar accompanying heating. Therefore, even if the heating temperature in the heating step is 150 ° C. or higher and lower than 230 ° C., it is presumed that the HGI and the pulverization rate are improved as compared with the non-heated Comparative Example A.
- Table 2 shows the cumulative ratio under sieving of the biomass solid fuel A subjected to the pulverization test
- FIG. 3 shows the particle size distribution.
- a pulverization test was performed. A 1 kg sample was placed in a resin bag from a height of 8.6 m and dropped 20 times, and then a rotational strength test was performed based on JIS Z 8841 to measure the particle size distribution. The obtained particle size distribution is shown in FIG. If the 2 mm sieve product in the sample particle size distribution is 30 wt% or less, and the 0.5 mm sieve product is 15 wt% or less, it is assumed that the particle size can be handled in transportation, storage, and the like. From Table 2 and FIG. 3, the sample particle size after the rotational strength test became finer as the solid temperature increased, but all the samples cleared the above-mentioned evaluation criteria, suggesting that they can be handled without problems. It was done.
- Table 3 and FIG. 4 show the results of an immersion test of biomass solid fuel A in water.
- the solid fuel of each Example and Comparative Example was immersed in water, taken out after a predetermined time shown in Table 3 and FIG. 4, wiped off the moisture, and the solid moisture was measured.
- the solid fuel of Comparative Example A (WP) was disintegrated by immersion in water, and measurement of solid moisture was impossible.
- the water content reached equilibrium in about 10 hours after immersion, and the equilibrium water content was about 27 wt%.
- the water content reached equilibrium after about 100 hours, and the equilibrium water content was about 25 wt%.
- Examples A-3 to A-5 were also equilibrated at a water content of about 23 wt% after about 100 hours.
- Example A-6 also almost reached equilibrium after about 100 hours, and the equilibrium water content was about 28 wt% (the fluctuation is larger than in Examples A-3 to A-5, but is considered to be due to variations in raw materials). .
- These results are thought to be because the surface of the biomass solid fuel changed to hydrophobic due to elution and solidification of organic components such as tar with heating.
- Examples A-1 to A-6 (PBT) are stored outdoors. As a solid fuel, there are advantageous characteristics as a solid fuel.
- FIG. 5 shows the results of measurement of solid strength before and after immersion in water (based on JIS Z 8841 rotational strength test method) for Examples A-1 to A-6 and Comparative Example A.
- Comparative Example A collapsed after being immersed in water, and thus the rotational strength after immersion was not measurable.
- Examples A-1 to A-6 (PBT) those obtained by wiping off the surface moisture of the solid fuel that reached the equilibrium moisture and drying it at 35 ° C. for 22 hours using a constant temperature dryer were used.
- FIG. 6 is a diagram showing the results of measuring the mechanical durability before and after immersion in water.
- the mechanical durability DU is expressed by the following formula in accordance with American agricultural industry standard ASAE S 269.4 and German industrial standard DIN EN 15210-1. Measured based on In the formula, m0 is the sample weight before the rotation treatment, m1 is the sample weight on the sieve after the rotation treatment, and a sieve using a plate sieve with a circular hole diameter of 3.15 mm was used.
- Example A-2 The evaluation was based on the “Spontaneous ignition test” of the “UN Test and Criteria Manual: Dangerous Goods Shipment and Storage Regulations 16th edition”. A measurement was made to determine whether 1 to 2 cm 3 of the biomass solid fuel (heating temperature 250 ° C.) of Example A-2 was dropped from a height of 1 m onto an inorganic heat insulating board and ignited within 5 minutes after dropping or within 5 minutes after dropping. I went twice. None of the six tests ignited, and Example A-2 (PBT) was determined not to fall under Container Class I in the United Nations Test and Criteria Manual.
- FIG. 7 is a graph showing the measurement result of the BET specific surface area of the solid fuel A.
- the sample was adjusted to 2 to 6 mm as a pretreatment. After being cut and filled into a container, vacuum deaeration was performed at 100 ° C. for 2 hours to obtain a BET specific surface area. Nitrogen gas was used as the adsorption gas.
- FIG. 7 shows that the BET specific surface area increases with increasing heating temperature, and that pores develop with heating (pyrolysis).
- FIG. 8 shows the average pore diameter on the surface of the solid fuel A
- FIG. 9 shows the total pore volume. Both the average pore diameter and the total pore volume were measured using the same apparatus as the BET specific surface area.
- the “pore” here is a pore having a diameter of 2 nm to 100 nm. Since the average pore diameter decreases with increasing heating temperature in Example A-2 and later, it shows that many fine pores are generated. This is believed to be due to cellulose degradation.
- FIG. 10 shows the yield (solid yield and heat yield) of biomass solid fuel A after the heating step.
- the solid yield is the weight ratio before and after heating
- the heat yield is the calorific value ratio before and after heating. Note that, as described above, holding at the target temperature (heating temperature) of each example is not performed (the same applies to Examples B to K below).
- biomass solid fuel A with reduced COD, improved grindability, reduced water absorption, improved solid strength, and improved yield is obtained at low cost. It was shown that
- the adsorption amount, generation amount, and H / C in the solid fuel of Example A-2 are as follows.
- FIG. 11 also shows SCI of bituminous coal in Table 4.
- the horizontal axis in FIG. 11 is arrival-based moisture, and the SCI of bituminous coal in FIG. 11 is prepared by adding moisture to the bituminous coal shown in Table 4 and preparing four types of samples each having different moisture. The SCI is calculated.
- the biomass solid fuel (PBT) of the present invention has a lower SCI (spontaneously exothermic) than bituminous coal and is comparable to high moisture bituminous coal. SCI (spontaneously exothermic). Thereby, it can be said that the biomass solid fuel A (PBT) of the present invention is a good fuel with reduced risk of ignition during handling.
- FIGS. 15 to 17 are cross-sectional SEM photographs before and after immersion in water in Comparative Example A (WP), FIG. 15 is before immersion, FIG. 16 is after immersion for 2 seconds, and FIG. 17 is after immersion for 20 seconds.
- the cross section after immersion is a cross section obtained by cutting the solid fuel after immersion for 2 seconds or 20 seconds. The magnification and scale are shown below each photo.
- Comparative Example A Comparative Example A (FIGS. 15 to 17)
- the pores are enlarged after immersion in water. Since this is a molded product of biomass in which Comparative Example A (WP) is pulverized as described above, it is presumed that the biomass was absorbed by water soaking and pores (gap between biomass powders) were enlarged. Accordingly, it is considered that the pulverized biomass is separated from each other by further intrusion of moisture into the enlarged pores, and the solid fuel itself collapses (see FIG. 4).
- WP Comparative Example A
- Example A-2 solid bridges develop between the biomass powders by heating, the hydrophobicity is improved and it is difficult to absorb water, and it is presumed that there is little change due to immersion. Therefore, even after immersion, since the connection or adhesion between the pulverized biomass by solid crosslinking is maintained, it is unlikely to collapse as in Comparative Example A. Therefore, in the heated solid fuels of Examples A-1 to A-6 (PBT), as shown in FIG. 4, biomass solids in which collapse due to rain water or the like is suppressed and handling properties during outdoor storage are ensured. Fuel has been obtained.
- Example B-1 to Example B-4 PBT
- the temperature was raised to the target temperature (heating temperature described in Table 5) in the same manner as in Example A except that European red pine was used as the raw material biomass. did.
- Tables 5 and 6 show properties of the solid biomass fuel B (Example B-1 to Example B-4) obtained after the heating step.
- Comparative example B (WP) was shown in the same manner.
- Example A no binder is used in any of Examples B-1 to B-4 and Comparative Example B. Since the moisture after immersion in water is after immersion for 100 hours or more (168 hours in Example B), it is considered that the moisture in the solid fuel B has substantially reached equilibrium.
- the measuring method of each property of the biomass solid fuel is the same as in Example A above.
- the ball mill grindability described in Table 6 was measured as follows.
- the pulverization time of each biomass solid fuel B was 20 minutes, and the weight ratio under a 150 ⁇ m sieve after 20 minutes was used as a pulverization point.
- the ball mill uses what conforms to JIS M4002, and uses a standard class ball bearing ( ⁇ 36.5 mm ⁇ 43, ⁇ 30.2 mm ⁇ 67, ⁇ 36.5 mm ⁇ 67 ⁇ 24.4 mm ⁇ 10 pieces, ⁇ 19.1 mm ⁇ 71 pieces, ⁇ 15.9 mm ⁇ 94 pieces), and rotated at a speed of 70 rpm for measurement. The higher the value, the better the grindability. It was confirmed that the pulverization point increased as the heating temperature increased.
- Comparative Example B disintegrated immediately after being immersed in water.
- the biomass powders were kept connected or adhered to each other even after being immersed in water (168 hours) and did not collapse.
- the solid shape was maintained after immersion, so that moisture measurement was possible and the expression of water resistance could be confirmed.
- pulverization is improved and COD is reduced as compared with Comparative Example B.
- Example B-3 is particularly excellent from the viewpoint of water resistance (moisture after immersion), and the biomass solid fuels of Examples B-2 and B-3 exhibit particularly excellent physical properties from the viewpoint of yield.
- Example B-2 is a fuel having excellent water resistance and pulverization properties and reduced COD based on the development of solid bridges.
- Example C The raw material biomass was heated to the target temperature (heating temperature described in Table 5) and heated (Example C-1 to Example C-4: PBT) in the same manner as in Example A, except that almond old wood was used. .
- the ball mill grindability was measured by the same method as in Example B above.
- Tables 5 and 6 show properties of the biomass solid fuel C obtained after the heating step.
- the water after immersion in water is considered to be balanced because it is after immersion for 100 hours or longer (168 hours in Example C).
- Comparative example C (WP) was shown in the same manner. In Examples C-1 to C-4 and Comparative Example C, no binder is used.
- Comparative Example C disintegrated immediately after being immersed in water.
- the connection or adhesion between the biomass powders is maintained even after being immersed in water, and the water resistance is improved without being destroyed.
- improvement in grindability and reduction in COD are shown.
- Example C-2, Example C-3 and Example C-4 are excellent, and from the viewpoint of thermal yield, Example C-1, Example C-2 and Example C- 3 is excellent.
- the HGI of Example C-1 is lower than that of Comparative Example C, but this is considered to be due to variations in raw materials and measurement errors, and it is estimated that there is at least an HGI equivalent to or higher than that of Comparative Example C. .
- Example D The raw material biomass was heated to the target temperature (heating temperature described in Table 5) and heated (Example D-1) in the same manner as in Example A, except that (30 wt% almond shell + 70 wt% almond old wood) was used.
- the ball mill grindability was measured by the same method as in Example B above.
- Tables 5 and 6 show properties of the biomass solid fuel D obtained after the heating step.
- the water after immersion in water is assumed to be balanced after immersion for 100 hours or more (168 hours in Example D). The same applies to Comparative Example D (WP). In Examples D-1 to D-4 and Comparative Example D, no binder is used.
- Comparative Example D disintegrated immediately after being immersed in water.
- Examples D-1 to D-4 the connection or adhesion between the biomass powders is maintained even after being immersed in water, so that they do not collapse and water resistance is improved.
- improvement in grindability and reduction in COD are shown.
- Examples D-2, D-3, and D-4 are excellent from the viewpoint of COD
- Examples D-1, D-2, and D-3 are particularly excellent from the viewpoint of thermal yield. showed that.
- Example E> The temperature was increased to the target temperature (heating temperature described in Table 5) in the same manner as in Example A, except that Acacia xylem was used as the raw material biomass, the biomass was molded into a tablet shape, and a ⁇ 70 mm tubular furnace was used as the heating device. Warmed and heated (Example E-1 to Example E-3: PBT). Properties of the biomass solid fuel E obtained after the heating step are shown in Tables 5 and 6. The water after immersion in water is considered to be balanced after immersion for 100 hours or more (168 hours in Example E). The same applies to Comparative Example E (WP). In Examples E-1 to E-3 and Comparative Example E, no binder is used.
- Example E the pH was measured by immersing the solid fuel at a solid-liquid ratio of 1:13.
- the immersion time of Comparative Example E in Table 6 indicates that the pH was measured, that is, the pH after 96 hours had elapsed after Comparative Example E was immersed.
- Example E Comparative Example E disintegrated immediately after immersion in water, but Examples E-1 to E-3 maintained water resistance without disintegration because the connection or adhesion between the biomass powders was maintained.
- Examples E-2 and E-3 are excellent from the viewpoint of water resistance (water after immersion in water), and Examples E-1 and E-2 are excellent from the viewpoint of heat yield.
- PBT heated at 240 to 270 ° C. is presumed to have formed the above-mentioned solid crosslinks, and is considered to have excellent water resistance, COD, pulverization properties, and the like. Further, the heat yield of Example E-1 exceeds 100%, but this is due to variations in raw materials and measurement errors.
- Example F The temperature was raised to the target temperature (heating temperature described in Table 5) and heated (Example F-1 to Example F-4: PBT) in the same manner as in Example E except that acacia bark was used as the raw material biomass.
- Tables 5 and 6 show the properties of the solid biomass fuel F obtained after the heating step.
- the water after immersion in water is considered to be balanced after immersion for 100 hours or more (168 hours or more in Example F).
- Comparative Example F WP
- no binder is used.
- Example F the pH was measured by immersing the solid fuel at a solid-liquid ratio of 1:13.
- the immersion time of Comparative Example F in Table 6 indicates that the pH was measured, that is, the pH after 96 hours had elapsed after Comparative Example F was immersed.
- Examples F-2, F-3, and F-4 are excellent from the viewpoint of COD and water resistance (moisture after immersion in water), and Examples F-1, F-2, and F are preferable from the viewpoint of thermal yield. -3 is excellent.
- Example G> The temperature was raised to the target temperature (heating temperature described in Table 5) in the same manner as in Example A except that (70 wt% almond shell + 30 wt% walnut shell) was used as the raw material biomass and a ⁇ 70 mm tubular furnace was used as the heating device. And heated (Example G-1 to Example G-4: PBT). Properties of the biomass solid fuel G obtained after the heating step are shown in Tables 5 and 6. Water after immersion in water is considered to be in equilibrium after being immersed for 100 hours or longer (144 hours or longer in Example G). The same applies to Comparative Example G (WP). In Examples G-1 to G-4 and Comparative Example G, no binder is used.
- Example G disintegrated immediately after being immersed in water, but Examples G-1 to G-4 maintained the connection or adhesion between the biomass powders and exhibited water resistance without disintegration.
- Examples G-2, G-3, and G-4 are excellent from the viewpoint of COD and water resistance (moisture after immersion in water), and Examples G-1 and G-2 and G are preferable from the viewpoint of thermal yield. -3 is excellent.
- the thermal yield of Example G-2 exceeds 100%, but this is due to variations in raw materials and measurement errors.
- Example H The sample was heated to the target temperature (heating temperature described in Table 5) and heated (Example H-1 to Example H-4: PBT) in the same manner as in Example A, except that sago palm was used as the raw material biomass.
- the ball mill grindability was measured by the same method as in Example B above. Properties of the biomass solid fuel H obtained after the heating step are shown in Tables 5 and 6.
- the water after immersion in water is considered to be balanced after immersion for 100 hours or more (168 hours in Example H).
- Comparative Example H (WP) In Examples H-1 to H-4 and Comparative Example H, no binder is used.
- the immersion time of Comparative Example H in Table 6 indicates that the pH was measured, that is, the pH after 24 hours had elapsed after Comparative Example H was immersed.
- Example H-1 to H-4 maintained water resistance without disintegration because the connection or adhesion between biomass powders was maintained.
- Example H-2, Example H-3, and Example H-4 are excellent from the viewpoint of COD, pH (slightly low) and water resistance (moisture after immersion in water), and Example H-1 and Example from the viewpoint of thermal yield H-2, example H-3, is excellent.
- Example I> The sample was heated to the target temperature (heating temperature described in Table 5) and heated (Example I-1) in the same manner as in Example A, except that EFB (empty fruit bunch of palm oil processing residue) was used as the raw material biomass.
- Example I-3 heated at 270 ° C. and Example I-4 heated at 300 ° C. was measured by the following method.
- a sample of 50 g is filled in a 1,000 cc polypropylene container, and is rotated with a MISUGI mixing man SKH-15DT at 60 rpm for 30 minutes (total 1,800 revolutions).
- m0 is the sample weight before the rotation treatment
- m1 is the sample weight on the sieve after the rotation treatment.
- Comparative Example I disintegrated immediately after immersion in water, but Examples I-1 to I-4 maintained the connection or adhesion between biomass powders and exhibited water resistance without disintegration.
- Examples I-2, I-3, and I-4 are excellent from the viewpoint of COD and water resistance (moisture after immersion in water), and Examples I-1, I-2, and I are excellent from the viewpoint of thermal yield. -3 is excellent.
- Example J The sample was heated to the target temperature (heating temperature described in Table 5) and heated (Example J-1, Example J-2: PBT) in the same manner as in Example A except that Meranti was used as the raw material biomass. Properties of the biomass solid fuel J obtained after the heating step are shown in Tables 5 and 6. The water after immersion in water is considered to be balanced after immersion for 100 hours or more (168 hours in Example J). The same applies to Comparative Example J (WP). In all of Examples J-1, J-2, and Comparative Example J, no binder is used.
- Example K The sample was heated to the target temperature (heating temperature described in Table 5) and heated (Example K) in the same manner as in Example A, except that a rubber tree was used as the raw material biomass and a ⁇ 70 mm tubular furnace was used as the heating device. -1).
- Table 5 shows properties of the biomass solid fuel K obtained after the heating step. The same applies to Comparative Example K (WP). In any case, no binder is used.
- Example K-1 As for the comparative example K, it is expected to collapse by immersion in water as in the other examples.
- Example K-1 the formation of the above-mentioned solid bridge is expected to improve water resistance, pulverization, reduce COD, etc. without being disintegrated even when immersed in water.
- Example K-1 is heated at 270 ° C., but the same effect can be estimated for a heating temperature of 230 to 270 ° C. as described above.
- the pellet diameters before and after immersion were measured by the same electronic caliper and measurement method as those in Table 7.
- Table 8 shows the measurement results.
- the measured value of the pellet diameter is an average value of 10 randomly selected in each of Examples A-1 to A-6.
- Tables 7 and 8 show that the expansion rate decreases as the temperature of the heating process increases. It is presumed that the expansion is suppressed by the formation of solid crosslinks accompanying heating. Although the radial expansion coefficient in Table 8 is higher than the length expansion coefficient in Table 7, this is because the immersion time is longer in Table 7, and because Example A is a pellet, it is mainly consolidated in the radial direction. Therefore, it is considered that the expansion also increases in the radial direction.
- the expansion coefficient is 10% or less even in Example A-1 having the largest radial expansion coefficient.
- the diameter and length expansion coefficient is preferably 10% or less, and more preferably 7% or less.
- the volume expansion coefficient is preferably 133% or less, and more preferably 123% or less.
- Example B is a pellet, and the diameter expansion coefficient calculated using the pellet diameter before immersion (initial dimension in Table 6) and the pellet diameter after immersion (dimension after immersion in Table 6) based on the formula (2) is It was 15% or less (hereinafter, the expansion coefficient of the diameter after Example B uses the formula (2)).
- the length expansion coefficient is smaller than the radial expansion coefficient in the pellet.
- the volume after immersion with respect to the volume of 100% is also the same for Example C and the following.
- the radial expansion coefficient is preferably 20% or less, and more preferably 10% or less.
- the volume expansion coefficient is preferably 173% or less, and more preferably 133% or less.
- Example C is also a pellet, and the volume expansion coefficient is 123% or less on the assumption that the diameter expansion coefficient before and after immersion is 7.2% or less and the length expansion coefficient is 7.2% at the maximum. Similarly, the volume expansion coefficient is calculated).
- the diameter expansion coefficient in Example C is preferably 13% or less, and more preferably 7% or less.
- the volume expansion coefficient is preferably 144% or less, and more preferably 123% or less.
- Example D pellet
- the expansion coefficient before and after immersion is 8.8% or less, and the volume expansion coefficient based on it is 129% or less.
- the diameter expansion coefficient in Example D is preferably 10% or less, and more preferably 8% or less.
- the volume expansion coefficient is preferably 133% or less, and more preferably 126% or less.
- Example E has a tablet shape, the diameter ( ⁇ ) expansion coefficient is 2.5% or less, the height (H) expansion coefficient is 40% or less, and the volume expansion coefficient is 147% or less.
- the radial expansion coefficient is preferably 5% or less, and more preferably 2.3% or less.
- the height expansion coefficient is preferably 50% or less, and more preferably 20% or less.
- the volume expansion rate is preferably 165% or less, and more preferably 126% or less.
- Example F has a diameter expansion coefficient of 4.0% or less, a height expansion coefficient of 15% or less, and a volume expansion coefficient of 124% or less. Note that the height after immersion in Example F-3 is considered to be a measurement error or individual variation.
- the expansion coefficient is preferably 5% or less, and more preferably 3% or less.
- the height expansion coefficient is preferably 40% or less, and more preferably 10% or less.
- the volume expansion coefficient is preferably 154% or less, and more preferably 117% or less.
- the expansion coefficient before and after immersion is 8.8% or less, and the volume expansion coefficient based on it is 129% or less.
- the expansion coefficient is preferably 10% or less, and more preferably 8% or less.
- the volume expansion coefficient is preferably 133% or less, and more preferably 126% or less.
- Example H pellet
- the expansion coefficient before and after immersion is 6.9% or less, and the volume expansion coefficient based on it is 122% or less.
- the radial expansion coefficient is preferably 10% or less, and more preferably 7% or less.
- the volume expansion coefficient is preferably 133% or less, and more preferably 123% or less.
- Example I pellets
- the expansion coefficient before and after immersion is 4.1% or less, and the volume expansion coefficient based on it is 113% or less.
- the expansion coefficient is preferably 10% or less, and more preferably 5% or less.
- the volume expansion rate is preferably 133% or less, and more preferably 116% or less.
- Example J the diameter expansion coefficient before and after immersion is 5.4% or less, and the volume expansion coefficient based on it is 117% or less.
- the expansion coefficient is preferably 20% or less, and more preferably 10% or less.
- the volume expansion coefficient is preferably 173% or less, and more preferably 133% or less.
- the solid fuel (PBT) of the present invention using biomass as a raw material preferably has an expansion coefficient of 40% or less before and after immersion (including diameter and height). Is preferably about 275% or less. More preferably, the expansion coefficient of diameter and length is 30% or less, and the volume expansion coefficient is about 220% or less. More preferably, the expansion coefficient of diameter and length is 20% or less, and the volume expansion coefficient is about 173% or less. More preferably, the expansion coefficient of diameter and length is 10% or less, and the volume expansion coefficient is about 133% or less.
- the biomass solid fuel (PBT) of the present invention does not collapse even by immersion and is shown to have water resistance.
Abstract
Description
燃料比(固定炭素/揮発分)が0.2~0.8、無水ベース高位発熱量が4800~7000(kcal/kg)、酸素Oと炭素Cのモル比O/Cが0.1~0.7、水素Hと炭素Cのモル比H/Cが0.8~1.3であり、バイオマス粉を成型したバイオマス固体燃料であることを特徴とする。
(米松、米栂、杉、および桧:固体燃料A)
本発明の一態様として、原料が米松、米栂、杉、および桧から選ばれる少なくとも1種を含む場合のバイオマス固体燃料(以下、固体燃料Aと記載することがある)の性状は以下のとおりである。
本発明の一態様として、原料が欧州アカマツである場合のバイオマス固体燃料(以下、固体燃料Bと記載することがある)の性状は以下のとおりである。
本発明の一態様として、原料がアーモンド古木である場合のバイオマス固体燃料(以下、固体燃料Cと記載することがある)の性状は以下のとおりである。
本発明の一態様として、原料がアーモンド殻とアーモンド古木の混合物である場合のバイオマス固体燃料(以下、固体燃料Dと記載することがある)の性状は以下のとおりである。
本発明の一態様として、原料がアカシア木部である場合のバイオマス固体燃料(以下、固体燃料Eと記載することがある)の性状は以下のとおりである。
本発明の一態様として、原料がアカシアバークである場合のバイオマス固体燃料(以下、固体燃料Fと記載することがある)の性状は以下のとおりである。
本発明の一態様として、原料がアーモンド殻と胡桃殻の混合物である場合のバイオマス固体燃料(以下、固体燃料Gと記載することがある)の性状は以下のとおりである。
本発明の一態様として、原料がサゴヤシである場合のバイオマス固体燃料(以下、固体燃料Hと記載することがある)の性状は以下のとおりである。
本発明の一態様として、原料がEFB(パーム油加工残渣の空果房)である場合のバイオマス固体燃料(以下、固体燃料Iと記載することがある)の性状は以下のとおりである。
本発明の一態様として、原料がメランティである場合のバイオマス固体燃料(以下、固体燃料Jと記載することがある)の性状は以下のとおりである。
本発明の一態様として、原料がゴムの木である場合のバイオマス固体燃料(以下、固体燃料Kと記載することがある)の性状は以下のとおりである。
(例A-1~A-6)
バイオマスを破砕後粉砕し、粉砕されたバイオマスを成型する成型工程およびその後の加熱工程を経てバイオマス固体燃料A(PBT)を得た。いずれの工程においてもバインダーは使用されない。原料のバイオマスとして、米松40重量%、米栂58重量%、杉1重量%、桧1重量%の混合物を用いた。各例の成型工程においては、直径8mmのペレット形状に成型した。各実施例における加熱工程ではφ600mm電気式バッチ炉にそれぞれの原料を4kg投入し、2℃/minの昇温速度で各実施例における目標温度(表1における加熱温度)まで昇温させ、加熱した。以下、目標温度と加熱温度は同一のものを指す。各例A-1~A-6いずれにおいても目標温度(加熱温度)における保持は行っていない(以下の例B~例Kも同様)。例A-1~A-6の加熱工程における加熱温度と、加熱工程後に得られたバイオマス固体燃料Aの性状を表1に示す。
比較例Aは破砕、粉砕後に成型したのみで加熱工程を経ていない、未加熱のバイオマス固体燃料(WP)である。比較例Aについてもバインダーは不使用である。原料のバイオマスは、例A-1と同様である。比較例Aの固体燃料の性状についても表1に示す。
図1は加熱工程における加熱温度と、得られたバイオマス固体燃料を水中に浸漬した際の浸漬水のCOD(化学的酸素要求量)およびpHの相関を示すものである(pHについては後述)。COD測定用浸漬水試料の調製は、昭和48年環境庁告示第13号(イ)産業廃棄物に含まれる金属等の検定方法に従い、CODはJIS K0102(2010)-17によって分析した。
例A-1~A-6および比較例Aの固体燃料を固液比1:3で浸漬し、pHを測定した。図1から、例A-2および例A-3については若干値が低くなるものの、全ての例A-1~A-6において概ねpHは6前後であり、加熱前の比較例Aと比べて特に変化はないことが示される。したがって、例A-1~A-6を屋外貯蔵した際に出る排水のpHについては特に問題ないことが示される。
図2は加熱工程における加熱温度と、得られたバイオマス固体燃料Aの粉砕性(HGI)、および粉砕速度(後述)の相関を、比較例Aおよび例A-1~A-6のバイオマス固体燃料について示す図である。
表2は粉化試験を行ったバイオマス固体燃料Aの篩下積算割合、図3はその粒度分布図である。ペレットのハンドリング特性を評価するために、粉化試験を実施した。サンプル1kgを8.6mの高さから樹脂製の袋に入れて20回落下させた後、JIS Z 8841に基づき回転強度試験を行い、粒度分布を測定した。得られた粒度分布を図3に示す。サンプル粒度分布における2mm篩下品が30wt%以下、および0.5mm篩下品が15wt%以下であれば搬送、貯蔵等におけるハンドリングが可能な粒度であるとみなすものとする。表2および図3より、回転強度試験後のサンプル粒度は固体温度が高くなるにつれて細かくなったが、いずれのサンプルにおいても上述の評価基準をクリアしており、問題無くハンドリング可能であることが示唆された。
表3および図4はバイオマス固体燃料Aの水中浸漬試験結果である。各実施例および比較例の固体燃料を水中に浸し、表3および図4に示す所定時間経過後に取り出して水分を拭き取って固体水分を測定した。比較例A(WP)の固体燃料は水中浸漬によって崩壊し、固体水分の測定は不可能であった。これに対し、例A-1の固体燃料では浸漬後約10時間で水分量が平衡に達し、平衡水分量は約27wt%であった。また、例A-2の固体燃料では約100時間経過後に水分量が平衡に達し、平衡水分は約25wt%であった。例A-3~A-5についても約100時間後に水分量約23wt%で平衡となった。例A-6も約100時間経過後にほぼ平衡に達し、平衡水分量は約28wt%であった(例A-3~A-5よりも振れが大きいが、原料のばらつきによるものと考えられる)。これらの結果は、加熱に伴うタール等有機成分の溶出・固化により、バイオマス固体燃料の表面が疎水性に変化したためと考えられ、例A-1~A-6(PBT)は屋外貯蔵されることが多い固体燃料として有利な特性を示している。
(回転強度)
図5は例A-1~A-6および比較例Aについて、水中浸漬前後の固体強度(JIS Z 8841 回転強度試験方法 に基づく)を測定した結果である。上述のとおり比較例A(WP)については水中浸漬後崩壊したため、浸漬後の回転強度は測定不可能であった。例A-1~A-6(PBT)については、平衡水分に達した固体燃料の表面水分を拭き取った後、恒温乾燥機にて35℃で22時間乾燥させたものを使用した。加熱工程を経た例A-1~A-6(PBT)の強度はほとんど低下しておらず、水中浸漬前の比較例A(WP)と比べても粉化が発生しにくく、ハンドリング性を維持できるものと言える。
図6は水中浸漬前後の機械的耐久性を測定した結果を示す図である。例A-1~A-6、比較例Aの固体燃料について、アメリカ農業工業者規格ASAE S 269.4、およびドイツ工業規格DIN EN 15210-1に準拠して機械的耐久性DUを以下の式に基づいて測定した。式中、m0は回転処理前の試料重量、m1は回転処理後の篩上試料重量であり、篩は円孔径3.15mmの板ふるいを用いた。
回転強度と同様、機械的耐久性についても加熱工程を経た例A-1~A-6(PBT)の強度はほとんど低下しておらず、水中浸漬前の比較例A(WP)と比べても粉化が発生しにくく、ハンドリング性を維持できることが示されている。
「国連試験および判定基準マニュアル:危険物船舶運送及び貯蔵規則16訂版」の「自然発火性試験」に基づき評価を行った。例A-2のバイオマス固体燃料(加熱温度250℃)1~2cm3を1mの高さから無機質断熱板上に落下させ、落下途中又は落下後5分以内に発火するか否かの測定を6回行った。6回の試験いずれも発火せず、例A-2(PBT)は上記国連試験および判定基準マニュアルの容器等級Iに該当しないと判定された。
自然発火性と同様、「危険物船舶運送及び貯蔵規則16訂版」の「自己発火性試験」に基づき評価を行った。試料容器(一辺が10cmのステンレス網立方体)に例A-2のバイオマス固体燃料(加熱温度250℃)を充填し、恒温槽内部に吊り下げ、140℃の温度で24時間連続して物質の温度を測定した。発火又は200℃を超える温度上昇の認められた物質は、自己発熱性物質と認め、更に一辺が2.5cmの試料容器を使用し同様の試験を行い、発火又は60℃を超える温度上昇の有無を確認した。試験結果に基づき、例A-2(PBT)は自己発熱性物質に該当しないと判定された。
(BET比表面積)
図7は固体燃料AのBET比表面積の測定結果を示す図である。例A-1~A-6および比較例Aの固体燃料につき、自動比表面積/細孔径分布測定装置(日本ベル(株)製BELSORP-min II)を用い、前処理として試料を2~6mmにカットして容器内に充填した後に、100℃で2時間真空脱気してBET比表面積を求めた。なお吸着ガスには窒素ガスを用いた。図7から、加熱温度の上昇に伴ってBET比表面積は増加しており、加熱(熱分解)にともなって細孔が発達していくことが示される。
図8は固体燃料A表面の平均細孔直径、図9は全細孔容積を示す図である。平均細孔直径、全細孔容積いずれもBET比表面積と同じ装置を用いて測定した。なお、ここでいう「細孔」とは直径2nm~100nmの孔とする。平均細孔直径は例A-2以降で加熱温度の上昇にともなって減少していることから、細かな細孔が多数生成していくことを示している。これはセルロースの分解に起因すると考えられる。
図10は加熱工程を経た後のバイオマス固体燃料Aの収率(固体収率および熱収率)である。固体収率は加熱前後の重量比、熱収率は加熱前後の発熱量比である。なお上述のとおり各実施例の目標温度(加熱温度)における保持は行っていない(以下の例B~例Kも同様)。
例A-2の固体燃料につき以下の方法で自然発熱性を測定した。試料1kgを容器に装入し、80℃の恒温槽中に反応器を入れて、試料に空気を流して得られたガスのO2、CO、CO2濃度を測定した。加熱前後の濃度から試料の加熱に基づくO2吸着量、CO発生量、CO2発生量を計算し、以下の式(1)に基づき自然発熱性指数(SCI)を算出する。
CO発生量 0.03[ml/kg・min]
CO2発生量 0.02[ml/kg・min]
H/C(例A-2の固体燃料における水素、炭素のモル比) 1.28[mol/mol](表1参照)
また、式(1)で用いた吸着熱、各生成熱は以下のとおりである。
CO生成熱 110.5[kJ/mol]
H2O生成熱 285.83[kJ/mol]
CO2生成熱 393.5[kJ/mol]
以上に基づき例A-2にかかる固体燃料のSCIを算出したところ、SCI=1.3であった。なお、本発明のバイオマス固体燃料Aは石炭に性状が近接していることから、O2吸着熱は石炭への吸着熱と同一のものを用いた。
図12~図14は例A-2における水中浸漬前後の固体燃料(PBT)の断面SEM写真である。図12は浸漬前、図13は2秒浸漬後、図14は20秒浸漬後である。同様に図15~図17は比較例A(WP)における水中浸漬前後の断面SEM写真であり、図15は浸漬前、図16は2秒浸漬後、図17は20秒浸漬後である。なお例A-2、比較例Aいずれも、浸漬後の断面とは2秒または20秒浸漬後の固体燃料を切断した断面のことである。また、各写真下に倍率およびスケールを示す。
例B-1~例B-4(PBT)においては、原料のバイオマスとして欧州アカマツを用いた以外は、例Aと同様にして目標温度(表5に記載の加熱温度)まで昇温させ、加熱した。加熱工程後に得られたバイオマス固体燃料B(例B-1~例B-4)の性状を表5及び表6に示す。比較例B(WP)についても同様に示した。なお例Aと同様、例B-1~例B-4、比較例Bいずれもバインダーは不使用である。水中浸漬後の水分は100時間以上浸漬後のものであるため(例Bでは168時間)、実質的に固体燃料B内の水分は平衡に達していると看做す。バイオマス固体燃料の各性状の測定方法は、上記例Aと同様である。なお、表6に記載のボールミル粉砕性は、下記のように測定した。
各バイオマス固体燃料Bの粉砕時間を20分として、20分後の150μm篩下の重量比を粉砕ポイントとした。なお、ボールミルはJIS M4002に準拠したものを用い、内径305mm×軸方向長さ305mmの円筒容器にJIS B1501に規定された並級ボールベアリング(Φ36.5mm×43個、Φ30.2mm×67個、Φ24.4mm×10個、Φ19.1mm×71個、Φ15.9mm×94個)を入れて70rpmの速度で回転させて測定した。数値が高い方が粉砕性は向上していることを示す。加熱温度の上昇にともない、粉砕ポイントは上昇することを確認した。
原料のバイオマスとして、アーモンド古木を用いた以外は、例Aと同様にして目標温度(表5に記載の加熱温度)まで昇温させ、加熱した(例C-1~例C-4:PBT)。ボールミル粉砕性については上記例Bと同様の方法で測定した。加熱工程後に得られたバイオマス固体燃料Cの性状を表5及び表6に示す。例Bと同様、水中浸漬後の水分は100時間以上の浸漬後(例Cでは168時間)であるため平衡しているものと看做す。比較例C(WP)についても同様に示した。なお例C-1~例C-4、比較例Cいずれもバインダーは不使用である。
原料のバイオマスとして、(30wt%アーモンド殻+70wt%アーモンド古木)を用いた以外は、例Aと同様にして目標温度(表5に記載の加熱温度)まで昇温させ、加熱した(例D-1~例D-4:PBT)。ボールミル粉砕性については上記例Bと同様の方法で測定した。加熱工程後に得られたバイオマス固体燃料Dの性状を表5及び表6に示す。水中浸漬後の水分は100時間以上の浸漬後(例Dでは168時間)であり、平衡しているものと看做す。また比較例D(WP)についても同様に示した。なお例D-1~例D-4、比較例Dいずれもバインダーは不使用である。
原料のバイオマスとしてアカシア木部を用い、バイオマスをタブレット形状に成型し、加熱装置としてφ70mmの管状炉を用いた以外は、例Aと同様にして目標温度(表5に記載の加熱温度)まで昇温させ、加熱した(例E-1~例E-3:PBT)。加熱工程後に得られたバイオマス固体燃料Eの性状を表5及び表6に示す。水中浸漬後の水分は100時間以上の浸漬後(例Eでは168時間)であり、平衡しているものと看做す。また比較例E(WP)についても同様に示す。なお例E-1~例E-3、比較例Eいずれもバインダーは不使用である。例EにおいてpHの測定は、固体燃料を固液比1:13で浸漬して測定した。ここで、表6における比較例Eの浸漬時間はpHを測定した時間、すなわち比較例Eを浸漬して96時間経過後のpHを測定したことを示す。
原料のバイオマスとしてアカシアバークを用いた以外は、例Eと同様にして目標温度(表5に記載の加熱温度)まで昇温させ、加熱した(例F-1~例F-4:PBT)。加熱工程後に得られたバイオマス固体燃料Fの性状を表5及び表6に示す。水中浸漬後の水分は100時間以上の浸漬後(例Fでは168時間以上)であり、平衡しているものと看做す。また比較例F(WP)についても同様に示す。なお例F-1~例F-4、比較例Fいずれもバインダーは不使用である。例FにおいてpHの測定は、固体燃料を固液比1:13で浸漬して測定した。ここで、表6における比較例Fの浸漬時間はpHを測定した時間、すなわち比較例Fを浸漬して96時間経過後のpHを測定したことを示す。
原料のバイオマスとして(70wt%アーモンド殻+30wt%胡桃殻)を用い、加熱装置としてφ70mmの管状炉を用いた以外は、例Aと同様にして目標温度(表5に記載の加熱温度)まで昇温させ、加熱した(例G-1~例G-4:PBT)。加熱工程後に得られたバイオマス固体燃料Gの性状を表5及び表6に示す。水中浸漬後の水分は100時間以上の浸漬後(例Gでは144時間以上)であり、平衡しているものと看做す。比較例G(WP)についても同様に示す。なお例G-1~例G-4、比較例Gいずれもバインダーは不使用である。
原料のバイオマスとしてサゴヤシを用いた以外は、例Aと同様にして目標温度(表5に記載の加熱温度)まで昇温させ、加熱した(例H-1~例H-4:PBT)。ボールミル粉砕性については上記例Bと同様の方法で測定した。加熱工程後に得られたバイオマス固体燃料Hの性状を表5及び表6に示す。水中浸漬後の水分は100時間以上の浸漬後(例Hでは168時間)であり、平衡しているものと看做す。比較例H(WP)についても同様に示す。なお例H-1~例H-4、比較例Hいずれもバインダーは不使用である。表6における比較例Hの浸漬時間はpHを測定した時間、すなわち比較例Hを浸漬して24時間経過後のpHを測定したことを示す。
原料のバイオマスとしてEFB(パーム油加工残渣の空果房)を用いた以外は、例Aと同様にして目標温度(表5に記載の加熱温度)まで昇温させ、加熱した(例I-1~例I-4:PBT)。加熱工程後に得られたバイオマス固体燃料Iの性状を表5及び表6に示す。水中浸漬後の水分は100時間以上の浸漬後(例Iでは168時間)であり、平衡しているものと看做す。比較例I(WP)についても同様に示す。なお例I-1~例I-4、比較例Iいずれもバインダーは不使用である。
DU=(m1/m0)×100
により機械的耐久性(DU)を算出した。式中、m0は回転処理前の試料重量、m1は回転処理後の篩上試料重量である。
原料のバイオマスとしてメランティを用いた以外は、例Aと同様にして目標温度(表5に記載の加熱温度)まで昇温させ、加熱した(例J-1、例J-2:PBT)。加熱工程後に得られたバイオマス固体燃料Jの性状を表5及び表6に示す。水中浸漬後の水分は100時間以上の浸漬後(例Jでは168時間)であり、平衡しているものと看做す。比較例J(WP)についても同様に示す。なお例J-1、例J-2、および比較例Jいずれもバインダーは不使用である。
原料のバイオマスとしてゴムの木を用い、加熱装置としてφ70mmの管状炉を用いた以外は、例Aと同様にして目標温度(表5に記載の加熱温度)まで昇温させ、加熱した(例K-1)。加熱工程後に得られたバイオマス固体燃料Kの性状を表5に示す。比較例K(WP)についても同様に示す。いずれもバインダーは不使用である。
PATとPBTの耐水性を比較するため、これらバイオマス固体燃料について、食塩水を用いて、吸水後のナトリウムの分布を調べた。PATの試料としては、原料の欧州アカマツを250℃で加熱した後直径6mmのペレットに成型した固体燃料を用いた。PBTの試料としては、原料の欧州アカマツを直径6mmのペレットに成型した後250℃で加熱した固体燃料(固体燃料B)を用いた。PBTとPATを0.9wt%の生理食塩水に5日間浸漬した。その結果、ペレット外観は図24に示したとおり、PBTはペレット形状を保持した(図24の左)が、PATは大きく崩壊した(図24の右)。また、PATおよびPBTを、それぞれ、生理食塩水に浸漬する前と0.9wt%の生理食塩水に5日間浸漬後について、その断面をEPMA(Electron Probe MicroAnalyser)分析にかけ、Na分布を比較した。Na分布は、PBTはペレット表面にとどまり内部に浸透していないのに対し、PATでは内部にまで広く分布していた(図25参照)。これはPBTの方がPATより生理食塩水の浸入が少ないことを意味する。この結果からも、PBTは隣接するバイオマス粉同士の間隙を抽出成分の熱分解物が固架橋し、疎水性になったために水の侵入を防いでいるのに対し、PATでは、バイオマス粉同士の間隙に水が浸入できるため水がペレット内部にまで浸透し、バイオマス粉同士の間隙を押し広げた結果、崩壊に至ったと推察される。
例A-1、A-3の固体燃料につき水中浸漬前後のペレット長さを測定した。ペレット長さについては、浸漬前のペレットを10個選択し、電子ノギス(ミツトヨ製:CD-15CX、繰り返し精度は0.01mmであり小数点2桁の部分を四捨五入した。)により測定するとともに、同じペレットを72時間水中浸漬させた後、再度電子ノギスにより長さを測定した。なお浸漬前後いずれにおいてもペレット端が斜めの場合は最も先端部分までを長さとして計測した。計測結果を表7に示す。表7に示すとおり、例A-1のペレット長さは平均で4.6%、例A-3は平均で0.2%増加した。
Claims (9)
- 燃料比(固定炭素/揮発分)が0.2~0.8、無水ベース高位発熱量が4800~7000(kcal/kg)、酸素Oと炭素Cのモル比O/Cが0.1~0.7、水素Hと炭素Cのモル比H/Cが0.8~1.3であること
を特徴とするバイオマス粉を成型したバイオマス固体燃料。 - 水中浸漬後、前記バイオマス粉同士の接続または接着が維持されること
を特徴とする請求項1記載のバイオマス固体燃料。 - COD(化学的酸素要求量)が3000ppm以下であること
を特徴とする請求項1または請求項2に記載のバイオマス固体燃料。 - バイオマスを成型して未加熱塊状物とし、この未加熱塊状物を加熱して得られること を特徴とする請求項1~3のいずれか1項に記載のバイオマス固体燃料。
- BET比表面積が0.15m2/g~0.8m2/gであること
を特徴とする請求項1~4のいずれか一項に記載のバイオマス固体燃料。 - 水中浸漬後の平衡水分が15~65wt%であること
を特徴とする請求項1~5のいずれか一項に記載のバイオマス固体燃料。 - バイオマスを成型して未加熱塊状物を得る成型工程と、
前記未加熱塊状物を加熱し、加熱済固体物を得る加熱工程と
を有し、
前記加熱済固体物をバイオマス固体燃料とするバイオマス固体燃料の製造方法であって、
前記加熱工程における加熱温度は、150℃~400℃であり、
燃料比(固定炭素/揮発分)が0.2~0.8、無水ベース高位発熱量が4800~7000(kcal/kg)、酸素Oと炭素Cのモル比O/Cが0.1~0.7、水素Hと炭素Cのモル比H/Cが0.8~1.3である、バイオマス固体燃料の製造方法。 - 前記未加熱塊状物の嵩密度をA、前記加熱済固体物の嵩密度をBとすると、B/A=0.7~1であること
を特徴とする請求項7に記載のバイオマス固体燃料の製造方法。 - 前記未加熱塊状物のHGI(ハードグローブ粉砕性指数)をH1、前記加熱済固体物のHGIをH2とすると、H2/H1=1.1~2.5であること
を特徴とする請求7または請求項8に記載のバイオマス固体燃料の製造方法。
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Also Published As
Publication number | Publication date |
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US20170218290A1 (en) | 2017-08-03 |
AU2018253504B2 (en) | 2019-07-25 |
AU2015329082A1 (en) | 2017-04-20 |
JPWO2016056608A1 (ja) | 2017-07-20 |
JP7289800B2 (ja) | 2023-06-12 |
JP2020090673A (ja) | 2020-06-11 |
KR102582930B1 (ko) | 2023-09-26 |
AU2018253504B9 (en) | 2019-08-08 |
US11390822B2 (en) | 2022-07-19 |
MY194667A (en) | 2022-12-12 |
CA2962744C (en) | 2023-02-21 |
AU2018253504A1 (en) | 2018-11-15 |
KR20230084598A (ko) | 2023-06-13 |
JP6648697B2 (ja) | 2020-02-14 |
CA2962744A1 (en) | 2016-04-14 |
MY179024A (en) | 2020-10-26 |
AU2015329082B2 (en) | 2018-08-23 |
KR102582926B1 (ko) | 2023-09-26 |
JP2022000527A (ja) | 2022-01-04 |
KR20170066511A (ko) | 2017-06-14 |
NZ730693A (en) | 2019-03-29 |
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